經濟部中央標率局負工消費合作杜印製 4 5 5 5 6 8 A7 B7 五、發明説明（1 ) 本發明領域 本發明有關針狀導電性氧化錫細粒，其製法，及其使 用方法，更特別關於一種可提供具有增加應用範圍和增加 附加價値之良好，高度功能物件之針狀導電性氧化錫細粒 Ο 相關技藝說明 已提出多種材料充作導電性賦予劑或塑料，橡膠，織 維等之抗靜電劑或充作記錄材料（諸如電子相影印紙，靜 電記錄紙等）載體之導電性賦予劑。例如，有已知針狀或 纖維導電性氧化錫細粒（例如，見J P_A - 5 6 -120519，JP-A_62-158199 及 JP — A - 5 - 1 1 7 9 0 6 )，含銻氧化錫球形顆粒（例如， 見JP-A - 4 — 77317)，導電性二氧化錫纖維（ 例如，見JP-A— 6 1-1 7 4 2 1 )，含二氧化鈦粉 末之導電性顆粒，其表面塗覆含氧化錫或氧化錫和氧化銻 之導電性層（例如，見JP - A - 5 6 — 4 1 6 0 3)， 表面塗覆有二氧化錫之纖維鈦酸鉀（例如，見J P — B — 6 1 - 2 6 9 3 3 )等。 因爲上述氧化錫，二氧化鈦顆粒或鈦酸鉀導電性顆粒 具有所謂電子導電型導電功能，故與離子導電材料比較， 諸如高分子電解質，其對濕度和溫度具有更高之導電性安 定性，且最近已發現可使用其充作多功能材料，諸如用於 提煉材料之導電性傳授劑，及不同領域（諸如塗料，油墨 本紙張尺度適用中國國家標準（CNS)A4規格（210X297公釐）_ 4 - (請先閱讀背面之注意事項再填寫本買〕 装· 455568 A7 B7 五、發明説明（2) ，塑料和纖維）之抗靜電物件以及，另外充作强化塡料。 其應用已經迅速地嚐試。 該導電性賦予劑係與橡膠，塑料，紙等結合，或分散 於含黏附劑之溶液中以製造一種塗覆溶液，隨後將該溶液 塗覆於不同的膜，板，載體，容器等。爲得到較佳導電性 ，必須增加該顆粒含量，因此至少相鄰之顆粒可緊密彼此 結合。因此，難以使用此種顆粒製造所需透明度之導電性 材料或導電性層。 此外，假如使用針狀或纖維狀導電性賦予劑，即使每 單位面積或體積使用少量導電性賦予劑，可有效地形成導 電途徑。但是’例如使用碳纖維，金屬毛，，金屬鬚等時 ，因這些係全部有色，故其不適於需要透明度或需要像紙 一樣白之用途。 經濟部中央橾率局員工消費合作社印製 --------裝-- (請先聞讀背面之注意事項再填寫本頁) ·" 爲解決這些問題，例如，已提出一種白色導電性材料 ，其包括一種塗覆有氧化錫傳導層之纖維狀酞酸鉀。其於 顆粒形狀上沒有問題，但其粉末電阻高且强度不符合。即 使該傳導層包含氧化錫和氧化銻，有一個問題係因其中含 鉀之綠故，難以製得具有低粉末電阻之所需材料。 此外，已知慣用導電性二氧化錫纖維係由一種非常緩 慢加熱且鍛燒草酸錫之方法製得（J P-A — 5 6 — 120519)，使用銅充作一種溶劑蒸發氧化錫，並將 該蒸汽導入低溫區以沈澱氧化錫之方法（j P — A — 6 2 —1 5 8 1 9 9 )，將一種使用錫化合物製備之結絲溶液 紡絲之（JP — A— 5-1 1 79 0 6 )等。但是，以這 本紙張尺度適用中國國家標準（CNS)A4規格（ 210X297公釐）-5_ A7 45 556 8 ___B7 五、發明説明（3 ) 些方法製得之產物又厚又長，例如，直徑〇· 5//m且長 度大約3mm，此外，其無法用於需要透明度之領域。此 外，這些方法包括於電子熔爐中熔融原材料，並由該熔化 物沈澱一種纖維產物，其需要長時間，且不適用工業製造 0 於上述導電性粉末材料之用途或應用中，近來，其需 要具有賦予所需導電性能力，例如，於避免使OHP膜， C RT窗，I C封裝及電子設備容器產生靜電，和用於液 晶顯示器和諸如E L體之透明電極，同時，其必須造成欲 處理材料表面大致上不吸收光，且可形成超薄之導電膜。 發明摘要 本發明目的係提出一種針狀導電性氧化錫細粒，其具 有適於賦予上述所需特性給不同用途領域材料之傳導性且 其透明度佳，該細粒製法和該細粒使用方法，以解決上述 問題。 上述目的可藉一種針狀導電性氧化錫細粒之製法，該 細粒平均直徑爲〇 . 0 0 5_ 1 ，平均長度爲 0. 〇5—10且縱橫比爲3或更高，該方法包括 於7 0 0 — 1 2 0 0 °C煅燒一種含錫，矽和一種鹼金屬鹵 化物之原材料並由該形成之煅燒材料去除可溶性鹽：一種 另外含銻之上述針狀氧化錫細粒製法達成，該方法包括將 一種銻化合物溶液加入上述針狀導電性氧化錫顆粒之懸浮 物中，然後進行中和作用，於該氧化錫細粒表面澱積水合 本紙張尺度適用中國國家標準（CNS)A4規格（ 210X297公釐）-6 - --------裝-------訂J------妹 (請先閲讀背面之注意事項再填寫本頁) · ” 經濟部中央標準局員工消費合作杜印製 經濟部中央標準局員工消費合作杜印裝 5 5 5 6 8 A7 B7五、發明説明（4) 氧化銻，之後將該經過濾且還原產物於7 0 0 — 1 〇 〇 〇 °c煅燒；針狀導電性氧化錫細粒之平均直徑爲0. 00 5 —l^m，平均長度爲〇· 05 — 10"m且縱橫比爲3 或更高，上述針狀導電性氧化錫細粒另外含銻，一種將上 述針狀導電性氧化錫細粒分散於一種水性介質製得之水性 分散液：一種將含銻之針狀氧化錫細粒分散於一種水性介 質製得之水性分散液：一種導電性組成物，其包括佔固體 物質1 0 Q重量份數之樹脂和3 _ 2 0 0重量份數之上述 針狀導電性氧化錫細粒或上述含銻之針狀導電性氧化錫細 粒0 附圖簡要說明 圖1係一電子顯微照相（X 1 〇 0 ，〇 〇 0 )，其顯 示本發明實施例4製得之針狀導電性氧化錫細粒之顆粒形 狀。 圖2係一電子顯微照相（X 1 〇 〇 ，〇 〇 0 )，其顯 示對照實例2之導電性細粒之顆粒形狀。 圖3係一電子顯微照相（X 1 〇 〇 ，〇 〇 〇 )，其顯 示於實施例11製得本發明含銻針狀導電性氧化錫細粒之 顆粒形狀。 圖4係一電子顯微照相（XI 0 〇 ，〇 〇 〇 )其顯示 對照實例5製得之導電性細粒之顆粒形狀。 較佳具體化實例詳細說明 --------裝-----I—訂J------冰 (請先閱讀背面之注意事項再填寫本頁) - 本紙张尺度適用中國國家標準（CNS)A4規格（ 210X297公嫠）-7 - 4 5 5 5 6 8 A7 經濟部中央橾準局員工消费合作社印製 __ B7五、發明説明（5 ) 爲嚐試提出一種解上述問題且符合上述表現之導電性 賦予劑，本發明者藉添加少量氧化錫細粒針狀以使該顆粒 於一種使用介質用容易彼此連績接觸，建構有效賦予導電 性之探索，其藉添加少量氧化錫細粒，使氧化錫細粒於一 種使用之介質中易於連續彼此接觸。結果，已發現（1 ) 當氧化錫細粒具有特殊平均長度，特殊平均直徑和大於特 殊値之縱橫比之針狀時，該氧化錫細粒可爲最適高度功能 材料，其可明顯賦予良好之傳導性，透明度和表面平滑， (2 )當氧化錫細粒係藉煅燒存在有鹼金屬鹵化幣之錫化 合物製得時，僅有矽組份存在時，未預期該氧化錫會變成 針狀，且上述（1 )中針狀氧化錫細粒之取適長度非常利 於工業製造，而且此外，該產物進行去除可溶性鹽之處理 ，其於多種用途之表現諸如導電性，透明度，表面光滑度 和黏附性佳，此外，當矽組份可維持一既定數置時，形成 之細粒於水中之分散性極佳，容易製得適於多種用途之水 性分散液，（3)於製造上述（2)之針狀氧化錫細粒之 第一步驟時，另外存在銻組份，可製得含銻之針狀導電性 氧化錫細粒，其導電性優於不含銻之針狀導電性氧化錫細 粒，及（4 )含銻針狀導電性氧化錫細粒，其大致上具有 非藍色顏色和高亮度，良好導電性和透明度及良好針狀性 ，其可藉在上述（2 )製得之針狀導電性氧化錫細粒表面 製造水性氧化銻，過濾並使該顆粒還原，且煅燒之。如此 ，完成本發明。 即，，本發明有關針狀導電性氧化錫細粒，其平均直徑Duty Printing Cooperative Work and Consumption Cooperation of the Central Standards Bureau of the Ministry of Economic Affairs 4 5 5 5 6 8 A7 B7 V. Description of the Invention (1) Field of the Invention The present invention relates to acicular conductive tin oxide fine particles, a method for preparing the same, and a method for using the same More specifically, a needle-shaped conductive tin oxide fine particle that can provide a good, highly functional object with increased application range and added value. Related technical descriptions have proposed a variety of materials to be used as conductivity imparting agents or plastics, rubber, and weaving. An antistatic agent such as Uygur or a conductivity imparting agent used as a carrier of recording materials (such as electronic photocopying paper, electrostatic recording paper, etc.). For example, there are known acicular or fibrous conductive tin oxide fine particles (see, for example, J P_A-5 6 -120519, JP-A_62-158199 and JP — A-5-1 1 7 9 0 6), containing antimony oxide Spherical tin particles (for example, see JP-A-4 — 77317), conductive tin dioxide fibers (for example, see JP-A — 6 1-1 7 4 2 1), conductive particles containing titanium dioxide powder, and their surfaces Coated with a conductive layer containing tin oxide or tin oxide and antimony oxide (see, for example, JP-A-56-4 1 6 0 3), and coated with fiber titanate of tin dioxide (see, for example, JP — B — 6 1-2 6 9 3 3) and so on. Because the above-mentioned tin oxide, titanium dioxide particles, or potassium titanate conductive particles have a so-called electronic conductivity type conductive function, compared with ionic conductive materials, such as polymer electrolytes, they have higher conductivity stability to humidity and temperature, and recently It has been found that it can be used as a multifunctional material, such as a conductive transfer agent for refining materials, and in different fields (such as coatings, inks, etc. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 4- (Please read the precautions on the back before filling in this purchase.) Equipment · 455568 A7 B7 V. Description of the invention (2), plastic and fiber) Anti-static objects and, in addition, used as reinforcing materials. Its application has been quickly tried. The conductivity imparting agent is combined with rubber, plastic, paper, or the like, or dispersed in an adhesive-containing solution to make a coating solution, and then the solution is applied to different films, plates, carriers, containers, etc. for To obtain better conductivity, the content of the particles must be increased, so that at least adjacent particles can be tightly bound to each other. Therefore, it is difficult to use such particles A conductive material or layer having a desired transparency can be created. In addition, if a needle-like or fibrous conductive agent is used, even if a small amount of conductive agent is used per unit area or volume, a conductive path can be effectively formed. However, for example When using carbon fiber, metal wool, metal must wait, because these are all colored, it is not suitable for applications that require transparency or need to be as white as paper. Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs --- --Install-- (Please read the notes on the back before filling this page) · " To solve these problems, for example, a white conductive material has been proposed, which includes a fibrous coating coated with a conductive layer of tin oxide Potassium phthalate. It has no problems with the shape of the particles, but its powder resistance is high and the strength does not match. Even if the conductive layer contains tin oxide and antimony oxide, there is a problem because it is difficult to obtain a low level because of the potassium-containing green. Materials required for powder resistors. In addition, it is known that conventional conductive tin dioxide fibers are produced by a very slow heating and calcining process of tin oxalate (J PA — 5 6 120519), using copper as a solvent to evaporate tin oxide, and introducing the steam into a low temperature region to precipitate tin oxide (j P — A — 6 2 — 1 5 8 1 9 9), a method using tin compounds Knotting solution spinning (JP — A— 5-1 1 79 0 6), etc. However, the Chinese national standard (CNS) A4 specification (210X297 mm) -5_ A7 45 556 8 _B7 5 is used for this paper size 3. Description of the invention (3) The products made by these methods are thick and long, for example, a diameter of 0.5 // m and a length of about 3 mm. In addition, they cannot be used in areas that require transparency. In addition, these methods are included in electronic furnaces Medium-melting raw materials, and precipitating a fiber product from the melt, which requires a long time, and is not suitable for industrial manufacturing. In the use or application of the above-mentioned conductive powder material, recently, it needs to have the ability to impart the required conductivity, such as In order to avoid causing static electricity to OHP film, C RT window, IC package and electronic equipment container, and used for liquid crystal display and transparent electrode such as EL body, at the same time, it must cause the surface of the material to be processed to not substantially absorb light. , And can form ultra-thin conductive film. SUMMARY OF THE INVENTION The object of the present invention is to provide acicular conductive tin oxide fine particles which have conductivity suitable for imparting the above-mentioned desired characteristics to materials in different fields of use and have good transparency. The method for preparing the fine particles and the method for using the fine particles, To solve the above problems. The above object can be achieved by a method for producing acicular conductive tin oxide fine particles, the average diameter of the fine particles is 0.05 to 5-1, the average length is 0.05 to 10, and the aspect ratio is 3 or higher. The method includes Calcining a raw material containing tin, silicon, and an alkali metal halide at 7 0 — 1 2 0 ° C and removing soluble salts from the formed calcined material: a method for preparing the above-mentioned acicular tin oxide fine particles additionally containing antimony The method includes adding an antimony compound solution to the above-mentioned acicular conductive tin oxide particle suspension, and then performing neutralization, and depositing hydration on the surface of the tin oxide fine particles. The paper is sized to the Chinese National Standard (CNS) A4. Specification (210X297mm) -6--------- install --------- order J ------ mei (please read the precautions on the back before filling this page) · "Economic Consumption cooperation between employees of the Central Standards Bureau of the Ministry of Printing and Printing Dumplings of employees of the Central Standards Bureau of the Ministry of Economic Affairs 5 5 5 6 8 A7 B7 V. Description of the invention (4) Antimony oxide, and then filtering and reducing the product to 7 0 0 — 1 000 ° C calcination; average diameter of acicular conductive tin oxide fine particles 0.005 —l ^ m, average length of 0.05—10 " m and aspect ratio of 3 or higher, the above-mentioned acicular conductive tin oxide fine particles additionally contain antimony, a kind of the above-mentioned acicular conductive tin oxide Aqueous dispersion prepared by dispersing fine particles in an aqueous medium: an aqueous dispersion prepared by dispersing acicular tin oxide fine particles containing antimony in an aqueous medium: a conductive composition including 1 0 Q parts by weight of resin and 3 _ 2 0 0 parts by weight of the above-mentioned acicular conductive tin oxide fine particles or the above-mentioned antimony-containing acicular conductive tin oxide fine particles 0 Brief description of the drawings Figure 1 is an electron microscope Photograph (X 100, 000), which shows the particle shape of the acicular conductive tin oxide fine particles prepared in Example 4 of the present invention. Figure 2 is an electron micrograph (X 1 000, 00). 0), which shows the particle shape of the conductive fine particles of Comparative Example 2. FIG. 3 is an electron micrograph (X 100, 000), which is shown in Example 11 to obtain the antimony-containing needle-like shape of the present invention. Particle shape of conductive tin oxide fine particles. Figure 4 is an electron micrograph (XI 〇 ， 〇〇〇〇) It shows the particle shape of the conductive fine particles prepared in Comparative Example 5. The preferred embodiment is explained in detail -------- 装 ----- I——J-- ---- Ice (please read the precautions on the back before filling this page)-This paper size is applicable to China National Standard (CNS) A4 (210X297) 嫠 -7-4 5 5 5 6 8 A7 Central Ministry of Economic Affairs 橾Printed by quasi-station employee consumer cooperatives __ B7 V. Description of the invention (5) In order to try to propose a conductivity imparting agent that solves the above problems and meets the above performance, the inventors have added a small amount of tin oxide fine particles in the shape of needles to make the particles In the use of a medium, it is easy to contact each other in succession, and the construction of effective conductivity is explored. By adding a small amount of tin oxide fine particles, the tin oxide fine particles are easy to continuously contact each other in a used medium. As a result, it has been found that (1) when the tin oxide fine particles have a special average length, a special average diameter, and a needle shape that is larger than a specific aspect ratio, the tin oxide fine particles can be an optimally highly functional material, which can obviously impart good Conductivity, transparency, and surface smoothness. (2) When tin oxide fine particles are prepared by calcining a tin compound containing an alkali metal halide coin, and only the silicon component is present, the tin oxide is not expected to become needle-like. And the appropriate length of the acicular tin oxide fine particles in (1) above is very conducive to industrial manufacturing, and in addition, the product is treated with soluble salts, and its performance in various uses such as conductivity, transparency, surface smoothness and adhesion Good performance, in addition, when the silicon component can be maintained at a predetermined number, the fine particles formed in the water have excellent dispersibility, and it is easy to prepare an aqueous dispersion suitable for various uses. (3) In the manufacture of the above (2) In the first step of acicular tin oxide fine particles, the antimony component is additionally present, and acicular conductive tin oxide fine particles containing antimony can be prepared, which has better conductivity than acicular conductive tin oxide fines without antimony. grain And (4) antimony-containing acicular conductive tin oxide fine particles, which have a substantially non-blue color and high brightness, good conductivity and transparency, and good acicularity, which can be obtained by the above (2) Aqueous antimony oxide is produced on the surface of the acicular conductive tin oxide fine particles, and the particles are filtered and reduced, and calcined. In this way, the present invention has been completed. That is, the acicular conductive tin oxide fine particles of the present invention have an average diameter
-.^1* —^^1 ί ^1^11 ^ϋ^—· n. - - I HI·--^^^^1 I I (請先閲讀背面之注意事項再填寫本頁) I 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐）-8 - 4 5 5 5 6 8 A7 經濟部中央橾隼局員工消費合作杜印製 _______B7五、發明説明（6 ) 爲0 〇〇5 — l"m和平均長度爲0. 0 5 — 10"m ，且縱橫比爲3或更高，較佳之針狀導電性氧化錫細粒平 均直徑爲0. 0 0 5 — Q. Q5"m和平均長度爲（3. 1 一 3"m，且縱橫比爲5或更高。本發明另外有關上述含 銻之針狀導電性氧化錫細粒。本發明另外有關該氧化錫細 粒之製法及使用該細粒之方法。本發明中使用之 ' 平均顆 粒大小(平均直徑和長度）係藉觀察一電子顯微照相（ XI 0 0 ，0 0 0 )得至之5 Owt%平均直徑大小。此 外，本發明使用之'^針狀顆粒〃包括纖維狀顆粒，柱狀顆 粒，棒條狀顆粒和除了該針狀顆粒之外在上述體積範圍內 類似形狀之顆粒。 本發明之針狀導電性氧化錫細粒可藉著於7 0 0 — 1 2 0 0 °C煅燒含錫，矽和鹼金屬鹵化物之原材料，然後 去除於該形成煅燒產物中之可溶性鹽製得。或者*該含銻 針狀導電性氧化錫細粒可藉煅燒該含錫，銻，矽和鹸金屬 鹵化物之原材料，然後去除該形成煅燒產物之可溶性鹽類 ，或藉於該針狀氧化錫顆粒之表面上澱積水合氧化銻充作 基質，然後煅燒之製得。 本發明之原材料含錫，矽和鹼金屬鹵化物，或含錫， 銻，矽和鹼金屬鹵化物，其中，不含一或多種非錫組份者 充作先質。 該原材料可以是將矽化合物和鹼金屬齒化物添加於包 括水合氧化錫之先質或其脫水產物中製得者；將鹼金屬鹵 化物添加於包括水含氧化錫先質，或其含矽脫水產物中製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-9 - (請先聞讀背面之注意事項存填寫本頁) 4 5 556 8 A7 經濟部中央橾準局員工消費合作社印製 _B7_五、發明説明（7 ) 得者：將水合氧化矽澱積於包括水合氧化錫先質或其脫水 產物表面上，然後於其中添加鹼金屬鹵化物製得者：將鹸 金屬齒化物添加於包括水合氧化錫先質或其含銻和矽之脫 水產物中製得者；將至少一種銻化合物和矽化合物及鹸金 屬鹵化物添加於包括水合氧化錫之先質或其含至少銻或錫 之一的脫水產物中製得者；或將水合氧化矽澱積於一種包 括水合氧化錫之基質或其含銻之脫水產物表面上，然後於 其中添加鹼金屬鹵化物製得者。 該包括一種錫化合物和一種较化合物，或一種錫化合 物，一種錫化合物和一種矽化合物之先質，其係藉不同方 法使用個別化合物或個別化合物溶液顆粒製備。例如，該 記述係由下列方法構成：（a )將一種錫化合物之水溶液 和一種矽化合物水溶液和一種鹼性水溶液同時個別加入 7 0 _ 9 0°C之熱水中進行中和作用，或將一種錫化合物 水溶液和一種銻化合物水溶液，以及一種矽化合物水溶液 和一種鹼水溶液同時個別加入7 0 - 9 0 °C熱水中進行中 和作用，（b )將一種鹼水溶液加入一種錫化合物水溶液 或一種錫化合物與一種銻化合物水溶液之混合水溶液中進 行中和作用，然後加入一種矽化合物水溶液，以調整其 pH至既定値，或添加膠狀二氧化矽，以及（c)將一種 錫化合物之水溶液加入一種鹼水溶液或將一種錫化合物水 溶液與一種銻化合物水溶液加入一種鹼水溶液中進行中和 作用，然後加入一種矽化合物水溶液以調整其P Η至給定 値或加入膠狀二氧化矽。這些方法中，方法（a )工業用 (請先聞讀背面之注意事項再填寫本頁) 裝· -55 本紙張尺度適用中國國家標準（CNS)A4規格（210X297公釐>-1〇 - A7 B7 4^556 8 五、發明説明（δ ) 較佳，且該實例中，將中和反應溶液之P Η維持在3或較 大値，以5-10較佳。 (請先閲讀背面之注意事項再填寫本頁) 該先質最好是藉同時個別添加氯化錫溶液或氯化錫溶 液與矽酸鈉溶液之氯化銻製備者。該先質中之銻組份最好 是以製造水合氧化錫系統中，中和或水解一種氯化錫水溶 液之鹼處理水合氧化銻製得之水合氧化銻組份較佳。 本發明中，製造水合氧化錫系統表示藉中和或水解上 述方法（a )〜（c )中之錫化合物水溶液製造該水合錫 氧化物之步驟，但其另外包括藉中和錫化合物和矽化合物 溶液製造氧化錫和二氧化矽水合物共沈澱物，和藉中和錫 化合物，銻化合物與矽化合物溶液製造氧化錫，氧化銻和 二氧化矽水合物之共沈澱物之實例。 該製得先質進行普通清洗，乾燥，磨光等，並於存在 鹼金屬鹵化物下以7 0 0 — 1 2 0 0煆燒。 當該先質與該鹼金藺鹵化物混合時，其可藉不同方法 ο 經濟部令失標隼局員工消費合作杜印製 進行。例如，如上述處理之先質與一種鹸金屬鹵化物可藉 一種混合攪拌器（諸如Heuschel混合器）混.合，當該形 成混合物以乾式粉磨機磨粉，可製得針狀度更佳之產物。 同時，可添加多種調整最終產物特性之調整劑。例如，爲 調整該針狀細粒之針狀度，可添加磷酸化合物，諸如磷酸 鉀。 可於7 0 0 — 1 2 0 0 °C進行煅燒，以8 0 0 — 1 1 0 0 °C較佳。若煅燒溫度低於7 0 0 °C，其針狀度不 充分，若高於1 2 0 0 °C，該顆粒直徑變大，且其透明度 本紙琅尺度適用中國國家標準（CNS) A4規格（ 210X297公釐> -- A7 455568 __ B7 五、發明説明（9 ) 易被破壞。該煆燒時間以3 0分鐘至5小時較適合。 (請先閱讀背面之注意事項再填寫本頁) 可使用不同鹼金屬鹵化物，實例爲氯化鈉，氯化鉀和 氯化鋰。該鹸金靥鹵化物佔該先質之Su〇2和S i 〇2 和Si〇2或Sn〇z ，Sb2〇3和Si〇2總重之1 %或更多，以1 0 — 1 0 〇%較佳。若該數量少於上述範 圍，其針狀度不充分.，而假如其太大，係經濟上之缺點， 另外，其生產性較差。使用鹼金屬鹵化物（諸如 B a C )替代鹼金屬鹵化物時，該顆粒可製成某種程 度之針狀，但其不足以與使用鹼金屬鹵化物時比較。 然後，將經煅燒產物以水或酸性水介質處理以去除可 溶性鹽。可使用不同酸充作該酸，諸如無機酸或有機酸， 較佳者係無機酸，諸如氫氯酸，硫酸和氫氟酸。 該經處理去除可溶性鹽之產物視情況需要進行離心沈 降處理*或以不同分類工具去除針狀度不足之顆粒，然後 進行一般過濾，清洗，乾燥，最終磨粉等，以製得一種含 銻之針狀導電性氧化錫細粒，其平均直徑爲0 . 0 0 5 - lpm，平均長度爲0 05 — 10"m，且其縱橫比爲 經濟部中央標準局員工消費合作社印製 5或更大者，至少佔總重7 0 %之粉末平均直徑爲 0. 003-lym，平均長度爲〇. 05-5;/m且縱 橫比5或更高者較佳。 該充作基質之針狀氧化錫顆粒可由本發明上述方法製 得，於該針狀氧化錫上澱積水合氧化銻可藉，例如將該針 狀氧化錫於溶劑（諸如水或一種醇）中分散以製備一種懸 浮液，於其中加入銻化合物之水溶液或醇溶液並搅拌進行 本纸張尺度適用中國國家標準{ CNS ) A4規格（210X297公釐）_ - 455568 A7 經濟部中央標準局員工消費合作社印裝 B7五、發明说明（10) 中和作用進行之。所需基質顆粒平均直徑爲〇. 〇〇5— li/m，以〇. Q0 5 — 0. 2"πι較佳，平均長度爲 〇 〇5-1〇只：11，以0. l-3"m較佳，縱橫比爲 3或更高，以5或更高者較佳。 本發明充作錫組份之錫化合物實例，該陳述係由錫鹵 化物（諸如氯化錫，氧化錫，氫氧化錫）’錫之無機酸鹽 (諸如，硫酸錫和硝酸錫（亞錫鹽和錫鹽））等。這些化 合物可單獨使用或二或多種摻和使用。氯化錫之氫氯酸水 溶液用途工業用較佳。 以矽化合物充作該矽組份時，除矽酸鈉之外，可使用 不同矽焼偶合劑，矽氧油，膠狀二氧化矽等。 與錫化合物混合之矽化合物數量最好佔S u 〇2重量 0. 3-20%，以0· 5-15%(以31〇2形態） 較佳。若數量少於0. 3%，無法製得該針狀度，即使其 添加量多於2 0 %，該添加效果不會增加，且無經濟上優 點。此外，最好添加大量至某種程度之矽化合物以得到良 好之針狀性，特別是，添加上述範圍內之數量銻化合物以 獲得較高傳導性時，亦添加上述範圍中較大數量之矽化合 物較佳。但是若大量矽化合物殘留於最終產物中，該導電 性受到不利影響，因此，藉由浸於氫氟酸等去除可溶性鹽 之處理去除不必要數量之矽化合物較佳。進行可溶性鹽去 除處理後，矽化合物殘留量丨占該產物中S η 〇2重置 〇 1 — 1 0 %，以 0 . 3 — 6 % (以 S i 〇 2 彤式）較 佳，該產物導電性優良，該產物於水中之分散性優良，且 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）ιη -1J · 裝------訂丨----- (請先閱讀背面之注意事項再填寫本頁) . A7 B7 455568 五、發明説明（11) 易得到適用多種用途之水性分散液。 (請先聞讀背面之注意事項再填寫本頁} 如該鹼水溶液中之鹼，陳述由例如鹼金屬之氫氧化物 和碳酸鹽及銨製得，諸如氫氧化鈉，氫氧化鉀，碳酸鈉和 碳酸鉀。這些化合物可個別單獨使用，或以二或多種摻和 物使用。該中和反應可於水，熱水或一種醇中進行，於熱 水中進行較佳。 如該銻化合物充作銻組份時，其陳述由例如銻鹵化物 (諸如氯化銻），氧化銻，氫氧化銻，和無機酸鹽（諸如 硫酸銻）製得。該化合物可個別單獨使用，或以二或多種 摻和物使用。一種氯化銻之氫氯酸水溶液係工業用較佳。 用於該錫化合物與銻化合物混合比時，原材料中之銻 組份數量佔Sn〇2重量之0. 1 — 8%，以（3. 3 — 5 % (以S b 2 0 3形式）較佳。該形成產物含銻量必須係 Sb/Sn 爲 0. 1/100 〜8/100，以 〇· 3/ 10 0 〜5/10 0較佳。若31)/31：<[). 1 / 1 〇 〇 ，無法得到所需導電性，若Sb/Sn>8/ 經濟部中夬標隼局員工消費合作社印製 1 0 0，無法得到直徑小且縱橫比高，且適於得到充分透 明度之所需針狀細粒。 此外，當水合銻氧化物澱積於針狀氧化錫顆粒表面充 作基質時，其澱積量佔Sn〇2重量之〇· 1 — 20%， 以1_1 5% (Sb2〇3形式）較佳。該形成產物含銻 量必須係Sb/Sn原子比0. 1/10Q — 2 0/ 1 0 0，以 1/1 〇 5/1 〇 〇 較佳。若 Sb/ S η < 0 . 1 / 1 0 0 ，無法得到所需傳導性，若s b / 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） A7 B7 455568 五、發明説明（1冷 S η >2 0/1 〇 〇 ，無法製得具有充分傳導性針狀細粉 末。 藉中和該銻化合物溶液於該針狀氧化錫顆粒上澱積水 合氧化銻可由不同方法進行，諸如下列方法：1 )將一種 銻化合物水溶液和一種鹼水溶液同時個別加入氧化錫分散 漿體中以進行中和作用，2)將一種銻化合物水溶液加入 氧化錫分散漿體中，然後加入一種鹼水溶液進行中和作用 ，及3 )將一種銻化合物水溶液加入氧化錫分散漿體中， 隨後將其加熱到沸點進行水解作用。上述方法1 ) - 2 ) 中，可於室溫進行該氧化錫分散漿體之添加作用，但是當 其於加熱下進行時，例如於7 Q - 9 G°C，可以更均勻地 澱積水合氧化銻，且其較佳。 當該鹼水溶液之鹼用於銻化合物之中和作用時，其陳 述係由例如，鹼金屬之氫氧化物和碳酸鹽及銨製得，諸如 ，氫氧化鈉，氫氧化鉀，碳酸鈉和碳酸鉀。這些化合物可 個別單獨使用或以二或多種摻和物使用。 其次，將水合氧化銻澱積於其上之形成產物過濾，清 洗且回收，並藉充分清洗和還原之鹼金屬組份充作中和劑 ，可藉下文提及之煅燒步驟中銻組份之作用更有效地發展 導電性。該還原產物視情況需要進行乾燥及磨粉，然後煆 燒之。該煅燒可於7 0 Q - 1 0 Q 0 T進行。若煅燒溫度 低於7 Q 0 Τ，導電性不充分，若其高於1 0 0 0 °C，該 細粒直徑大，且無法維持其原始形狀。煅燒時間以3 〇分 鐘至5小時較適合。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉_ 15 _ I- ^^1 II ^^1 1^1 HI ^^1 I— - - - Hr ^^1 Jn I ^ (請先鬩讀背面之注意事項#填筠本買) . 經濟部中央標隼局買工消費合作社印製 A7 45556 8 B7 五、發明説明（ (請先閱讀背面之注意事項再填寫本頁) 本發明針狀導電性氧化錫細粒或含銻之針狀導m性氧 化錫細粒係與塑料，橡膠，纖維等結合，充作導電性賦予 劑或充作使其爲導電性組成物（諸如，導電性塑料，導電 性塗料，磁性塗料，導電性橡膠，和導電性纖維）之基質 。導電性塑料實例中，可使用不同塑料，諸如所謂一般用 途塑料和工程用塑料。一般用途塑料之實例係聚乙烯，氣 化乙烯樹脂，聚苯乙烯，聚丙烯，甲基丙烯酸樹脂和腺， 三聚氟妓樹脂。包括於工程用塑料之一般用途塑料實例係 一種酚樹脂，不飽和聚酯樹脂，剛性氯化乙烯樹脂、 經濟部中央標準局員工消費合作杜印裝 A B S樹脂和A S樹脂。工程用塑料實例係一種環氧樹脂 ，聚縮醛，聚碳酸酯，聚對酞酸伸丁酯，聚對酞酸伸乙酯 ，聚伸苯醚，聚伸苯硫醚，聚亞砚和氟碳樹脂。超工程用 塑料之實例係酞酸二烯丙酯樹脂，矽氧樹脂，聚醯亞胺樹 月旨，聚醢胺醯亞胺，雙三聚氛胺三嗪，聚胺基雙三聚氰胺 ，烯烴-乙烯基醇共聚物，聚氧化笮烯，聚甲基戊烯，聚 醚亞硕，聚醚醯亞胺，聚芳酯和聚醚酮，添加於上述模製 樹脂之針狀導電性氧化錫細粒之數量爲1 0 0重量份數樹 脂中，3 — 2 0 0重量份數，以1 0 — 1 0 0重量份數較 佳。 使用本發明針狀導電性氧化錫細粒或含銻針狀導電性 氧化錫細粒充作導電塗料或磁性塗料，其與不同黏合劑結 合，諸如聚乙烯醇樹脂，氯化乙烯，醋酸乙烯酯樹脂，丙 烯酸樹脂，環氧樹脂，胺酯樹脂，醇酸樹脂，聚酯樹脂， 醋酸伸乙基乙烯基共聚物，丙烯基-苯乙烯共聚物，膠態 本紙張尺度適用中國國家標準（CNS ) A4規格（2)0X297公釐） 經濟部中央標隼局員工消費合作杜印裝 4 5 5 5 6 8 A7 __B7 五、發明説明（1今 樹脂，酚樹脂，胺基樹脂，氟碳樹脂，矽氧樹脂，石油樹 脂和天然樹脂，諸如蟲膠，松脂衍生物和橡膠衍生物，及 將形成混合物於水或溶劑中分散◊加入該黏著劑樹脂之針 狀導電性氧化錫細粒數量係每1 Q 〇重量份數黏著劑固體 物質中3 — 2 0 0重量份數，以1 〇 — 1 〇 〇重量份數。 該導電性塗料實例中，將該塗料塗覆於絕緣基質（諸如， 紙或聚合物膜）上，形成一種導電性塗層，其重量輕，且 透明性，表面平滑性和鈷附性優良，因此可製得不同抗靜 電膜，靜電記錄紙，電子照相複印紙等。該針狀導電性氧 化錫細粒施加於一種水性塗料時，於水性介質中之氧化錫 細粒製造步驟中，藉分散該氧化錫細粒或自該氧化錫細粒 去除可溶性鹽製得之餅（cake )，製備一種水性分散液 ，並使用該形成水性分散液充作塗料，節省塗料製造中所 需之分散能量和製造該氧化錫細粒步驟中所需之脫水和乾 燥能量。該水性分散液之固體濃度爲1 _ 7 Q重量％，以 1 〇_5 0重量％較佳，該水性分散液pH値爲4 一 1 2 ，以5 — 1 0較佳。 將氧化錫細粒施加於該塗料以製備磁性記錄介質時， 其有利於介於非磁性載體和磁性層間的黏著性之改善，避 免該磁性記錄介質之靜電char gnig ，加强膜强度，薄化 該磁性層，改善較低非磁性層之分散性以使表面平滑，表 面光滑性改善。尤其是，近來磁性記錄有明顯趨勢以增加 記錄密度，此外，縮短記錄波長。就此目的，更强烈需求 係薄化該磁性記錄介質之磁性層。但是，但是當該磁性層 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨Ο X 297公釐）-17 — !| II ---In —i- -- m ϋ - I I I I -I -Γ I I I I 咏 (請先閱讀背面之注意事項再填寫本頁) 4 5 556 8 A7 ____B7 五、發明説明（4 薄化時，該載體影響易顯現於磁性層表面，且電磁轉化特 性不可避免地惡化。因此，於該非磁性載體表面提出一非 磁性底塗層，之後提出一種磁性層充作上層，因此，解決 該載體表面粗糙性問題，另外薄化該磁性層以增加產出。 本發明，與較低非磁性層結合之針狀導電性氧化錫細粒比 例大約爲2 0 — 8 0體積％。 導電性橡膠實例中，氧化錫細粉末與慣用已知橡膠結 合，諸如矽氧橡膠，異戊二烯橡膠，苯乙烯-丁二烯橡膠 ，丁二烯橡膠，丁基橡膠，丁二烯一丙烯腈橡膠，乙烯一 丙烯一二乙烷聚合物，乙烯-丙烯橡膠，氟橡膠，乙烯_ 醋酸乙烯酯共聚物，氯化聚乙烯，丙烯酸樹脂，氯丁二烯 橡膠，胺酯橡膠，聚硫醚橡膠，氯磺化聚乙烯樹脂，和3 —氯_1 ，2 —環氧丙烷橡膠。 充作導電性纖維實例中，氧化錫細粒與聚醯胺樹脂， 聚酯樹脂，聚烯烴樹脂，聚乙烯樹脂和聚醚樹脂等之可紡 織纖維結合。 經濟部中夾標準局員工消费合作社印製 (請先閲讀背面之注意事項再填寫本頁) 如此製得之導電性組成物可添加比包括球形導電性顆 粒之慣用導電性組成物更少量之樹脂黏著劑，得到高度導 電性，另外，其透明性較佳且有經濟上優點。因爲本發明 針狀氧化錫細粒之數量較少*可使用該顆粒不會使黏著劑 之强度降低。此外，高濃度導電性塗料實例中，即使塗覆 薄塗層亦可得到所需傳導性。特別是，使用於針狀氧化錫 顆粒上澱積水合氧化物製得之含銻針狀氧化錫細粒時，該 產物出人意料地消除bluish色調，具有優良傳導性和透 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ _ 經濟部中央標準局員工消費合作社印製 455568 A7 ______ B7五、發明説明（1句 明度。 玆以下列實施例例證本發明。 實施例1 將5 0 0 g之五水四氯化錫溶解於5 0 之3N 氫氯酸溶液中製備之溶液，1 7. 4mi?之矽酸鈉水溶液 (3 0 8 g / j?之S i 0 2形式）與氫氧化鈉同時個別於 2 0分鐘內加入5 $ 9 0°C之純水，保持該系統之pH於 7-7. 5以製造一種其沈澱物。然後，於其中加入氪氯 酸將該系統p Η調整至3，之後過濾該沈澱物，並以水清 洗，直到該濾液之電阻率達到1 5 Q Ο Ο Ω c m爲止。該 形成之胼於1 1 Q °C乾燥1 2小時，將2 0重量份數氯化 鈉加入1 0 0重量份數之乾燥產物中，隨後，均勻混合之 並硏磨該混合物。該混合物於電爐中以9 0 0 °C煅燒1小 時。其後，形成之煅燒產物浸於一種氫氟酸水溶液中去除 可溶性鹽，接著乾燥並硏磨之製得所需之針狀導電性氧化 錫細粒。 實施例2 以實施例1之相同方法製造所需之針狀導電性氧化錫 細粒，但是使用3 4 . 9 m $之矽酸鈉水溶液。 實施例3 使用氯化鉀替代氯化鈉，以同實施例1之方法製造所 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標隼（CNS ) A4規格（210x297公釐） 455568 A7 B7 經濟部中夬標準局—工消費合作社印裝 五、發明説明（1乃 需之針狀導電性氧化錫細粒。 實施例4 以同實施例1之方法製得所需之方法製得所需之針狀 導電性氧化錫細粒，但其煅燒溫度爲1 Q Q 〇 °c。該產物 之電子顯微照相示於圖1 。 實施例5 將3 0 0 g五水四氯化錫溶解於3 0 0 m j? 3 N氫氯 酸水溶液中製得之溶液與一種濃度爲2 0 0 g/5之氫氧 化鈉溶液於2 0分鐘期間同時個別加入5又9 0 °C之純水 中，維持該系統pH爲7. 0 - 8 . 0以產生一種沈澱物 。然後，於其中加入氫氯酸調整該系統p Η至3，之後過 濾該沈澱物，並以水沖洗直到濾液之電阻率爲2 0 0 0 0 Ω cm爲止。形成之餅於1 2 0°C乾燥1 2小時，並以磨 粉器硏磨。於100重量份數經硏磨產物中加入2. 5重 量份數之膠態二氧化矽和2 0重量份數之氯化鈉，隨後混 合之製得一均勻混合物。該混合物於電爐中以9 0 0 °C煅 燒1小時。之後，形成之乾燥產物浸於氫氟酸水溶液中去 除可溶性鹽，隨後乾燥並硏磨之，製得所需之針狀導電性 氧化錫細粒。 實施例6 ' 以同實施例1之方法製得所需之針狀導電性氧化錫細 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 裝------訂一*------^ (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（1珍 粒，但氯化鈉之數量爲6 0重量份數。 對照實例1 以同實施例1之方法製造導電性細粒，但不使用氯化 鈉。 對照實例2 以同實施例1之方法製造導電性細粒，但不使用矽酸 鈉。該產物之電子顯微照相示於圖2。 對照實例3 以同實施例1之方法製造導電性細粒，但其煅燒溫度 爲 6 0 0 °C。 實施例7 將500g五水四氯化錫和3. 36g之三氯化銻溶 於3 N氫氯酸水溶液中製備之溶液，17. 4m_?之矽酸 經濟部中央標準局員工消費合作杜印製 (請先閱讀背面之注意事項再填寫本頁) 鈉水溶液（3 0 8 g /又之S i 0 2形式）與氫氧化鈉溶 液同時個別於2 0分鐘期間內加入5 Θ 9 0 °C之純水，保 持該系統之pH於7—7. 5以製造一種其沈澱物。然後 ，於其中加入氫氯酸將該系統p Η調整至3 ，之後過濾該 沈澱物，並以水清洗，直到該濾液之電阻率達到 1 5 0 0 〇ncm爲止。該形成之餅於1 1 0°C乾燥1 2 小時，將2 0重量份數氯化鈉加入1 Q Q重量份數之乾燥 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 21 455568 A7 B7 五、發明説明（1守 產物中，隨後，均勻混合之並硏磨該混合物。該混合物於 電爐中以9 0 0 °C煅燒1小時。其後，形成之煅燒產物浸 於一種氫氟酸水溶液中去除可溶性鹽，接著乾燥並硏磨之 製得所需之含銻針狀導電性氧化錫細粒。顆粒顏色b_値 (於2 0 0kg/cm3壓粒下塡充）爲一 9. 4,其値 L *爲 7 3 . 6 〇 實施例8 以同實施例7之方法製得所需之含銻針狀導電性氧化 錫細粒，但該三氯化銻數量爲10. lg。 實施例9 以同實施例7之方法製得所需之含銻針狀導電性氧化 錫細粒，但使用3 4 . 9 m $之矽酸鈉水溶液。 實施例1 0 經濟部申央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 以同實施例7之方法製得所需之含銻針狀導電性氧化 錫細粒，但是以氯化鉀替代氯化鈉。 實施例1 1 以同寅施例7之方法製得所需之含銻針狀導電性氧化 錫細粒，但是其煅燒產物爲1 0 〇 〇°C。該產物電子顯微 照相示於圖3。 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇χ297公釐）说 4 5 5 5 6 8 經濟部中央標準局員工消費合作社印製 A7 ______B7_ 五、發明説明（叫 實施例1 2 將3 0 0 g五水四氯化錫與2 . 0 2 g之三氯化銻溶 解於3 0 Omp 3 N氬氯酸水溶液中製得之溶液與一種濃 度爲2 0 0 g/又之氫氧化鈉溶液於2 0分鐘期間同時個 別加入5又9 0 °C之純水中，維持該系統p Η爲7 . 0 — 8. 0以產生一種沈澱物。然後，於其中加入氫氯酸調整 該系統ρ Η至3 ，之後過濾該沈澱物，並以水沖洗直到濾 液之電阻率爲2 0 0 0 ODcm爲止。形成之餅於1 2 0 °C乾燥1 2小時，並以磨粉器硏磨。於1 Q 0重量份數經 硏磨產物中加入2. 5重量份數之膠態二氧化矽和20重 量份數之氯化鈉，隨後混合之。該混合物於電爐中以 9 0 0 °C煅燒1小時。之後，形成之乾燥產物浸於氫氟酸 水溶液中去除可溶性鹽，隨後乾燥並硏磨之，製得所需之 含銻針狀導電性氧化錫細粒。 實施例1 3 以同實施例7之方法製得所需之含銻針狀導電性氧化 錫細粒，但該氯化鈉數量爲6 (3重量份數。 對照實例4 以同實施例7之方法製得導電性細粒，但不使用氯化 鈉0 對照實例5 ^紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ μ _ --------- 裝------訂^------^ (請先閱讀背面之注意事項再填寫本頁) _ 5 556 8 A7 B7 五、發明説明（21) 以同實施例7之方法製得之導電性細粒，但不使用矽 酸鈉。該產物之電子顯微照相示於圖4。 對照實例6 以同實施例7之方法製得導電性細粒，但使用3 7 g 之三氯化銻。 對照寅例7 以同寅施例7之方法製得導電性細粒，但其煅燒溫度 爲 6 0 0 °C。 對照實例8 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 將234. 5g之五水四氯化錫和15. 6g之三氯 化銻溶解於5 0 Omi?之5 N氫氯酸水溶液中製備之溶液 ，9. 7m义之矽酸鈉水溶液（308g/5之Si〇2 形式）與氫氧化鈉溶液同時個別於3 0分鐘期間內加入5 又9 0°C之純水，保持該系統之pH於6 — 7以製造一種 氧化錫，氧化銻和二氧化矽水合物之共沈澱物。然後，於 其中加入氫氯酸將該系統pH調整至3 ，之後過濾該沈澱 物，並以水清洗，直到該濾液之電阻率達到1 5 Ο 0 Ο Ω cm爲止。該形成之餅於7 0 Q°C乾燥4小時，且將乾燥 產物以磨粉器硏磨之，製得比表面積爲75. 6rrf/g之 球形細粒。 本紙張尺度適用中國國家標隼（CNS ) A4規格（2丨ΟX 297公釐） 〇 ^ -24 A7 4 5 5 5 6 8 B7 五、發明説明（0 實施例1 4 (請先閱讀背面之注意事項再填寫本頁) 將5 0 0 g之五水四氯化錫溶解於5 0 OmJ?之3N 氫氯酸水溶液中製備之溶液，17. 4m{之矽酸鈉水溶 液（3 0 8 g/j?之S i 〇2形式）與氫氧化鈉溶液同時 個別於2 0分鐘內加入5 ί 9 0°C之純水，保持該系統之 Η於7—7. 5以製造一種其沈澱物。然後，於其中加入 氫氯酸將該系統pH調整至3，之後過濾該沈澱物，並以 水清洗，直到該濾液之電阻率達到1 5 0 0 OQcni爲止 。該形成之餅於1 1 0°C乾燥1 2小時，將2 0重量份數 氯化鈉加入1 0 0重量份數之乾燥產物中，隨後，均匀混 合之並硏磨該混合物。該混合物於電爐中以9 0 0 °C烺燒 1小時。其後，形成之煅燒產物浸於一種氫氟酸水溶液中 去除可溶性鹽。然後，將該形成之餅於5 純水中再製成 漿，且加熱至9 0°C。然後，於其中在2 0分鐘期間內同 時個別加入由將3. 36g三氯化銻（Sb/Sn原子比 爲1/1 0 0 )溶解於3 0 0m$ 3N氫氯酸水溶液中製 得之溶液與氫氧化鈉溶液，保持該系統p Η爲7 _ 7 . 5 經濟.那中央標準局員工消費合作杜印製 ，以將水合氧化銻澱積於針狀氧化錫上。然後，加入氫氯 酸調整該系統ρ Η値爲3，之後過濾該沈澱物並以水清洗 ，直到該濾液電阻率達到2 0 0 Ο 0Ω cm爲止。該形成 餅於電爐中以9 0 0 °C煅燒1小時，並以磨粉機硏磨，製 得本發明含銻針狀氧化錫細粒。 實施例I 5 本紙張尺度適用中國國家標準（CNS ) A4规格（210X 297公釐）oc zb - A7 4 5 556 8 - 五、發明说明（23) 以同實施例14之方法製得本發明含鍊針狀氧化錫細 粒，但於澱積水合氧化銻後，該經過濾且還原餅之媳燒溫 度爲 1 0 0 0 °C。 實施例1 6 以同實施例14之方法製得本發明含銻之針狀氧化錫 細粒，但該三氯化銻之數量爲16. 8 2 g ( S b / S η 原子比爲5 / 1 Ο Ο )。 試驗實例1 以上述實施例和對照實例製得之導電性細粒樣本建構 下列測量。（1 )該重量平均顆粒大小係觀察電子顯微照 相（XI 0 0，0 0 0 )而得，此外，縱橫比亦由其計算 出。（2 )該樣本粉末之電阻率係於1 〇 〇 k g/cm3 壓力下以數位 multi meter 測量：Yokogawa Hokushin Electric Cq. Ltd 製之 Model 2 5 0 2A。結果示於表 1。 -1 i m In ^^1 ^^1 I - - - - —1 ^^^1 - 1^1----( ^ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 29?公釐） 45 556 8 A7-. ^ 1 * — ^^ 1 ί ^ 1 ^ 11 ^ ϋ ^ — · n.--I HI ·-^^^^ 1 II (Please read the precautions on the back before filling this page) I Paper The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -8-4 5 5 5 6 8 A7 Printed by the Consumer Cooperation Department of the Central Government Bureau of the Ministry of Economic Affairs _______B7 V. Invention Description (6) is 0 〇〇 5 — l " m and an average length of 0. 0 5 — 10 " m and an aspect ratio of 3 or higher, and the preferred needle-shaped conductive tin oxide fine particles have an average diameter of 0. 0 0 5 — Q. Q5 " m and the average length is (3.1 to 3 " m, and the aspect ratio is 5 or higher. The present invention further relates to the above-mentioned acicular conductive tin oxide fine particles containing antimony. The present invention also relates to the tin oxide fine particles. Preparation method and method for using the fine particles. The average particle size (average diameter and length) used in the present invention is obtained by observing an electron micrograph (XI 0 0, 0 0 0) to obtain an average diameter of 5 wt% In addition, the "acicular particles" used in the present invention include fibrous particles, columnar particles, rod-shaped particles, and other types of particles in the above-mentioned volume range in addition to the acicular particles. Shape-like particles. The acicular conductive tin oxide fine particles of the present invention can be calcined at 7 0 — 1 2 0 ° C, and then the raw materials containing tin, silicon and alkali metal halides are calcined and then removed to form a calcined product. It can be obtained by dissolving the soluble salt. Or * The antimony acicular conductive tin oxide fine particles can be calcined the raw materials containing tin, antimony, silicon and thallium metal halide, and then remove the soluble salts forming the calcined product, or It is prepared by depositing hydrated antimony oxide as a matrix on the surface of the acicular tin oxide particles, and then calcining. The raw materials of the present invention contain tin, silicon and alkali metal halides, or tin, antimony, silicon and alkali metals. Halides, in which one or more non-tin components are not used as precursors. The raw materials may be those obtained by adding a silicon compound and an alkali metal dentate to a precursor including hydrated tin oxide or a dehydrated product thereof; The alkali metal halide is added to the water containing tin oxide precursor or its silicon-containing dehydration product. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -9-(Please read the note on the back first Matter filling (This page) 4 5 556 8 A7 Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs_B7_ V. Description of Invention (7) Winner: Deposit hydrated silicon oxide on the surface of the precursor containing hydrated tin oxide or its dehydrated product Prepared by adding an alkali metal halide to it: prepared by adding a hafnium metal dentate to a hydrated tin oxide precursor or its dehydrated product containing antimony and silicon; at least one antimony compound and a silicon compound and鹸 metal halide prepared by adding a precursor containing hydrated tin oxide or a dehydrated product containing at least one of antimony or tin; or depositing hydrated silicon oxide on a substrate containing hydrated tin oxide or an antimony containing The dehydrated product is prepared by adding an alkali metal halide to the surface. This includes a tin compound and a comparative compound, or a tin compound, a tin compound, and a precursor of a silicon compound, which are prepared by using different methods using individual compounds or individual compound solution particles. For example, the description is composed of the following methods: (a) adding an aqueous solution of a tin compound, an aqueous solution of a silicon compound, and an aqueous alkaline solution to the hot water at 70 ° -90 ° C, respectively, for neutralization, or An aqueous solution of a tin compound and an aqueous solution of an antimony compound, and an aqueous solution of a silicon compound and an aqueous alkali solution are separately added to hot water at 70-90 ° C for neutralization. (B) An aqueous alkaline solution is added to an aqueous tin compound or A tin compound and an antimony compound aqueous solution are used for neutralization, and then a silicon compound aqueous solution is added to adjust its pH to a predetermined level, or colloidal silicon dioxide is added, and (c) an tin compound aqueous solution is added. Add an alkaline aqueous solution or an tin compound aqueous solution and an antimony compound aqueous solution to an alkaline aqueous solution for neutralization, and then add a silicon compound aqueous solution to adjust its P Η to a given 値 or add colloidal silicon dioxide. Among these methods, method (a) for industrial use (please read the precautions on the back before filling this page). -55 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm > -1〇- A7 B7 4 ^ 556 8 V. The description of the invention (δ) is better, and in this example, the P 中 of the neutralization reaction solution is maintained at 3 or larger, preferably 5-10. (Please read the back page first) Please note this page before filling in) This precursor is best prepared by adding antimony chloride solution of tin chloride solution or tin chloride solution and sodium silicate solution at the same time. The antimony component in the precursor is preferably based on In the production of a hydrated tin oxide system, a hydrated antimony oxide component prepared by neutralizing or hydrolyzing an aqueous solution of tin chloride with alkali treatment of hydrated antimony oxide is preferred. In the present invention, the production of a hydrated tin oxide system means neutralizing or hydrolyzing the above method. (A) ~ (c) The step of manufacturing the hydrated tin oxide by the tin compound aqueous solution, but it additionally includes manufacturing a tin oxide and silicon dioxide hydrate coprecipitate by neutralizing the tin compound and a silicon compound solution, and borrowing Soluble with tin compounds, antimony compounds and silicon compounds An example of manufacturing co-precipitates of tin oxide, antimony oxide, and silicon dioxide hydrate. The prepared precursor is subjected to ordinary cleaning, drying, polishing, etc., and in the presence of an alkali metal halide at 7 0 0 — 1 2 0 0 煆. When the precursor is mixed with the alkali metal halide, it can be printed by different methods. Ο The Ministry of Economic Affairs has ordered the employee to cooperate with the printing process. For example, the precursor treated as described above and a kind of 鹸The metal halides can be mixed and mixed by a mixing mixer (such as a Heuschel mixer). When the formed mixture is pulverized with a dry mill, a product with better needle shape can be obtained. At the same time, various characteristics can be added to adjust the characteristics of the final product For example, in order to adjust the needle shape of the needle-like fine particles, a phosphoric acid compound, such as potassium phosphate, can be added. It can be calcined at 7 0 — 1 2 0 0 ° C, and 8 0 0 — 1 1 0 0 ° C is preferred. If the calcination temperature is lower than 700 ° C, the needle shape is insufficient. If it is higher than 120 ° C, the particle diameter becomes larger, and the transparency of the paper is in accordance with Chinese national standards. (CNS) A4 size (210X297mm >-A7 455568 __ B7 5. Description of the invention (9) It is easy to be destroyed. The burn time is more suitable for 30 minutes to 5 hours. (Please read the precautions on the back before filling this page) Different alkali metal halides can be used, an example is chlorination Sodium, potassium chloride, and lithium chloride. The osmium halide accounts for 1% of the total weight of the precursors Su〇2 and Si 02 and Si 02 or SnOz, Sb203 and Si02. Or more, it is preferably 10 to 100%. If the amount is less than the above range, the needle degree is insufficient. If it is too large, it is an economic disadvantage and in addition, its productivity is poor. When an alkali metal halide (such as B a C) is used instead of the alkali metal halide, the particles can be made to a certain degree of needle shape, but it is not enough to compare with the case where an alkali metal halide is used. The calcined product is then treated with water or an acidic aqueous medium to remove soluble salts. Various acids can be used as the acid, such as an inorganic acid or an organic acid, more preferably an inorganic acid, such as hydrochloric acid, sulfuric acid, and hydrofluoric acid. The processed product for removing soluble salts may be subjected to centrifugal sedimentation treatment * if necessary, or particles with insufficient needleness may be removed by different classification tools, and then subjected to general filtration, washing, drying, and final grinding to obtain an antimony-containing product. Needle-shaped conductive tin oxide fine particles, the average diameter of which is 0. 0 0 5-lpm, the average length is 0 05 — 10 " m, and its aspect ratio is 5 or greater printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Or, at least 70% of the total weight of the powder has an average diameter of 0.003-lym, an average length of 0.05-5; / m and an aspect ratio of 5 or higher is preferred. The acicular tin oxide particles used as a matrix can be prepared by the above method of the present invention. The hydrated antimony oxide can be deposited on the acicular tin oxide, for example, the acicular tin oxide is dissolved in a solvent such as water or an alcohol. Disperse to prepare a suspension, add aqueous solution or alcohol solution of antimony compound to it and stir for paper size Applicable to Chinese National Standard {CNS) A4 (210X297 mm) _-455568 A7 Staff Consumer Cooperative of Central Standards Bureau, Ministry of Economic Affairs Printing B7 V. Description of Invention (10) The neutralization effect is carried out. The required average diameter of the matrix particles is 0.005—li / m, preferably 0. Q0 5—0.2 " πm, and the average length is 0.005 to 10: 11, 0.1 to 3 " m is preferred, the aspect ratio is 3 or higher, and 5 or higher is preferred. The present invention is an example of a tin compound as a tin component. The statement is based on a tin halide (such as tin chloride, tin oxide, tin hydroxide), an inorganic acid salt of tin (such as tin sulfate, and tin nitrate (stannous salt). And tin salt)) etc. These compounds may be used alone or in combination of two or more. Hydrochloric acid aqueous solution of tin chloride is preferred for industrial use. When a silicon compound is used as the silicon component, in addition to sodium silicate, different silica gel couplers, silicone oil, and colloidal silicon dioxide can be used. The amount of the silicon compound mixed with the tin compound is preferably 0.3 to 20% by weight, and more preferably 0.5 to 15% (in the form of 3102). If the amount is less than 0.3%, the needle shape cannot be obtained, and even if the addition amount is more than 20%, the addition effect will not increase, and there is no economic advantage. In addition, it is best to add a large amount of silicon compound to a certain degree to obtain good needle shape. In particular, when adding an amount of antimony compound in the above range to obtain higher conductivity, a larger amount of silicon in the above range is also added. Compounds are preferred. However, if a large amount of silicon compound remains in the final product, the conductivity is adversely affected. Therefore, it is preferable to remove an unnecessary amount of the silicon compound by immersion in a hydrofluoric acid or the like to remove a soluble salt. After the soluble salt removal treatment, the residual amount of the silicon compound 丨 accounts for S η 〇2 reset in the product 〇1-10%, preferably 0.3-6% (in the form of Si02), the product Excellent electrical conductivity, the product has excellent dispersibility in water, and this paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) ιη -1J · Equipment -------- Order 丨 ----- (Please read the precautions on the back before filling out this page). A7 B7 455568 V. Description of the invention (11) It is easy to obtain aqueous dispersions suitable for various uses. (Please read the notes on the back before filling this page} If the alkali in the alkaline aqueous solution, state that it is made from, for example, hydroxides and carbonates of alkali metals and ammonium, such as sodium hydroxide, potassium hydroxide, sodium carbonate And potassium carbonate. These compounds can be used individually or in admixtures of two or more kinds. The neutralization reaction can be performed in water, hot water or an alcohol, preferably in hot water. When used as an antimony component, its statement is made of, for example, antimony halides (such as antimony chloride), antimony oxide, antimony hydroxide, and inorganic acid salts (such as antimony sulfate). The compounds can be used individually or in two or 1 — — A variety of admixtures are used. An antimony chloride aqueous hydrochloric acid solution is preferred for industrial use. When the tin compound is mixed with the antimony compound, the amount of antimony component in the raw material accounts for 0.1% of the weight of Sn〇2. 8%, preferably (3.3-5% (in the form of S b 2 0 3). The antimony content of the formed product must be Sb / Sn from 0.1 / 100 to 8/100, and 0.3 / 10 0 to 5/10 0 is preferred. If 31) / 31: < [). 1/1 〇〇, the required conductivity cannot be obtained, Sb / Sn > 8 / Economic section Jue standard consumer cooperative Falcon Office employee printed 100, a small diameter can not be obtained and a high aspect ratio, and is adapted to obtain the desired acicular fine particles of sufficient transparency. In addition, when the hydrated antimony oxide is deposited on the surface of the acicular tin oxide particles as a matrix, the deposition amount accounts for 0.1-20% of the weight of Sn02, preferably 1_15% (in the form of Sb203). . The antimony content of the formed product must be Sb / Sn atomic ratio of 0.1 / 10/10 to 2/1 0 0, more preferably 1/1 0 5/1 0 0. If Sb / S η < 0.1 / 1 0 0, the required conductivity cannot be obtained, if sb / this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 455568 V. Description of the invention ( 1 Cold S η > 2 0/1 00, it is impossible to obtain needle-like fine powder with sufficient conductivity. The precipitation of hydrated antimony oxide on the needle-like tin oxide particles by neutralizing the antimony compound solution can be performed by different methods, Methods such as: 1) adding an antimony compound aqueous solution and an alkaline aqueous solution simultaneously to the tin oxide dispersion slurry for neutralization, 2) adding an antimony compound aqueous solution to the tin oxide dispersion slurry, and then adding an alkaline aqueous solution Performing neutralization, and 3) adding an antimony compound aqueous solution to the tin oxide dispersion slurry, and then heating it to a boiling point for hydrolysis. In the above methods 1)-2), the tin oxide dispersion slurry can be added at room temperature, but when it is performed under heating, for example, at 7 Q-9 G ° C, the hydration can be more uniformly deposited. Antimony oxide is preferred. When the base of the alkaline aqueous solution is used for neutralization of antimony compounds, the statement is made from, for example, hydroxides and carbonates of alkali metals and ammonium, such as sodium hydroxide, potassium hydroxide, sodium carbonate and carbonic acid. Potassium. These compounds may be used individually or in admixtures of two or more kinds. Second, the product formed by the deposition of hydrated antimony oxide on it is filtered, washed and recovered, and the alkali metal component fully washed and reduced is used as a neutralizing agent. The antimony component in the calcination step mentioned below can be used as a neutralizer. Function to develop conductivity more effectively. The reduced product is dried and ground as necessary, and then burned. The calcination can be performed at 70 Q-10 Q 0 T. If the calcination temperature is lower than 7 Q 0 T, the conductivity is insufficient. If it is higher than 1000 ° C, the fine particles have a large diameter and cannot maintain their original shape. The calcination time is preferably 30 minutes to 5 hours. This paper size applies to China National Standard (CNS) A4 (210X297 mm) _ 15 _ I- ^^ 1 II ^^ 1 1 ^ 1 HI ^^ 1 I—---Hr ^^ 1 Jn I ^ (Please First read the precautions on the back #Fill in this purchase). Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Buyers and Consumer Cooperatives A7 45556 8 B7 V. Description of the invention ((Please read the precautions on the back before filling out this page) The present invention Needle-shaped conductive tin oxide fine particles or needle-shaped m-conductive tin oxide fine particles containing antimony are combined with plastics, rubber, fibers, etc., and act as a conductivity imparting agent or as a conductive composition (such as, Conductive plastic, conductive coating, magnetic coating, conductive rubber, and conductive fiber). In the example of conductive plastic, different plastics can be used, such as so-called general-purpose plastics and engineering plastics. Examples of general-purpose plastics are Polyethylene, vaporized ethylene resin, polystyrene, polypropylene, methacrylic resin and gland, trifluorofluororesin resin. General purpose plastics included in engineering plastics. Examples are a phenol resin, unsaturated polyester resin, rigid Chlorinated vinyl resin, economic Consumers' cooperation of the Central Bureau of Standards Du printed ABS resin and AS resin. Examples of engineering plastics are an epoxy resin, polyacetal, polycarbonate, polybutylene terephthalate, polyethyl terephthalate, poly Polyphenylene oxide, polyphenylene sulfide, polymethylene, and fluorocarbon resin. Examples of super engineering plastics are diallyl phthalate resin, silicone resin, polyimide tree, polyimide Amines, bis trimeramine triazines, polyamine bis melamines, olefin-vinyl alcohol copolymers, polyoxyalkylenes, polymethylpentenes, polyethers, polyethersimines, polyarylates Polyetherketone, added to the resin of the needle-shaped conductive tin oxide fine particles of the above molding resin in an amount of 100 parts by weight, 3 to 2 0 parts by weight, and 10 to 10 parts by weight Preferably, the acicular conductive tin oxide fine particles or antimony-containing acicular conductive tin oxide fine particles of the present invention are used as a conductive coating or a magnetic coating, which are combined with different adhesives such as polyvinyl alcohol resin, vinyl chloride, Vinyl acetate resin, acrylic resin, epoxy resin, amine ester resin, alkyd resin, Ester resin, ethylene vinyl acetate copolymer, propylene-styrene copolymer, colloidal This paper size applies to Chinese National Standard (CNS) A4 specifications (2) 0X297 mm Du printed 4 5 5 5 6 8 A7 __B7 V. Description of the invention (1 resin, phenol resin, amine resin, fluorocarbon resin, silicone resin, petroleum resin and natural resin, such as shellac, turpentine derivatives and rubber Derivatives, and the amount of acicular conductive tin oxide fine particles added to the adhesive resin are dispersed in water or a solvent, and the amount is 3-2 0 0 parts by weight per 1 Q 0 parts by weight of the solid material of the adhesive. In terms of 100-1000 parts by weight. In the example of the conductive coating, the coating is coated on an insulating substrate (such as paper or a polymer film) to form a conductive coating, which is lightweight, transparent, and has excellent surface smoothness and cobalt adhesion. Therefore, different antistatic films, electrostatic recording paper, electrophotographic copy paper, etc. can be prepared. When the acicular conductive tin oxide fine particles are applied to an aqueous coating, in a tin oxide fine particle manufacturing step in an aqueous medium, a cake prepared by dispersing the tin oxide fine particles or removing soluble salts from the tin oxide fine particles (Cake), preparing an aqueous dispersion, and using the aqueous dispersion to form a coating, to save the dispersion energy required in the manufacture of the coating and the dehydration and drying energy required in the step of manufacturing the tin oxide fine particles. The solid concentration of the aqueous dispersion is 1 to 7 Q% by weight, preferably 10 to 50% by weight, and the pH of the aqueous dispersion is 4 to 12, preferably 5 to 10. When tin oxide fine particles are applied to the coating to prepare a magnetic recording medium, it is beneficial to improve the adhesion between the non-magnetic carrier and the magnetic layer, avoid the electrostatic char gnig of the magnetic recording medium, strengthen the film strength, and thin the film. Magnetic layer, improving the dispersibility of the lower non-magnetic layer to make the surface smooth and the surface smoothness improved. In particular, there has been a recent trend in magnetic recording to increase the recording density and, in addition, to shorten the recording wavelength. For this purpose, there is a stronger demand for thinning the magnetic layer of the magnetic recording medium. However, when the paper size of the magnetic layer is in accordance with the Chinese National Standard (CNS) A4 specification (2 丨 〇 X 297 mm) -17 —! | II --- In —i--m ϋ-IIII -I- Γ IIII (Please read the precautions on the back before filling this page) 4 5 556 8 A7 ____B7 V. Description of the invention (4 When the thickness is reduced, the carrier effect is easy to appear on the surface of the magnetic layer, and the electromagnetic conversion characteristics inevitably deteriorate Therefore, a non-magnetic base coat is proposed on the surface of the non-magnetic carrier, and then a magnetic layer is proposed as the upper layer. Therefore, the surface roughness of the carrier is solved, and the magnetic layer is thinned to increase the output. The present invention, and The proportion of acicular conductive tin oxide fine particles combined with a lower non-magnetic layer is about 20 to 80% by volume. In the case of conductive rubber, the fine tin oxide powder is combined with a conventionally known rubber such as silicone rubber, isoprene Diene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, butadiene-acrylonitrile rubber, ethylene-propylene-diethylene polymer, ethylene-propylene rubber, fluorine rubber, ethylene_acetic acid Vinyl ester copolymer , Chlorinated polyethylene, acrylic resin, chloroprene rubber, urethane rubber, polysulfide rubber, chlorosulfonated polyethylene resin, and 3-chloro_1, 2-propylene oxide rubber. Filled as conductive fibers In the example, the tin oxide fine particles are combined with textile fibers such as polyamide resin, polyester resin, polyolefin resin, polyethylene resin, and polyether resin. Printed by the Consumer Cooperative of the China Standards Bureau of the Ministry of Economic Affairs (please read first) Note on the back, please fill in this page again.) The conductive composition thus prepared can be added with a smaller amount of resin adhesive than the conventional conductive composition including spherical conductive particles to obtain high conductivity, and in addition, its transparency is better. And there are economic advantages. Because the number of acicular tin oxide fine particles of the present invention is small * the use of the particles will not reduce the strength of the adhesive. In addition, in the case of high-concentration conductive coatings, even thin coatings are applied. The required conductivity can be obtained. In particular, when antimony-containing acicular tin oxide fine particles prepared by depositing a hydrated oxide on acicular tin oxide particles are used, the product unexpectedly eliminates the bluish hue, Excellent conductivity and transparent paper size Applicable to China National Standard (CNS) A4 specifications (210X297 mm) _ _ Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 455568 A7 ______ B7 V. Description of the invention (1 sentence clarity. Examples illustrate the present invention. Example 1 A solution prepared by dissolving 500 g of tin tetrapentapentahydrate in 50 N 3N hydrochloric acid solution, 17.4 mi? Of sodium silicate aqueous solution (3 0 8 g / j? In the form of S i 0 2) Simultaneously add 5 $ 9 0 ° C pure water separately in 20 minutes with sodium hydroxide, keeping the pH of the system at 7-7. 5 to make a precipitate Thing. Then, chlorochloric acid was added to adjust the system p Η to 3, and then the precipitate was filtered and washed with water until the resistivity of the filtrate reached 1 5 Q 〇 Ω c m. The formed mash was dried at 11 Q ° C for 12 hours, and 20 parts by weight of sodium chloride was added to 100 parts by weight of the dried product, followed by uniformly mixing and honing the mixture. The mixture was calcined in an electric furnace at 900 ° C for 1 hour. Thereafter, the formed calcined product was immersed in an aqueous hydrofluoric acid solution to remove soluble salts, and then dried and honed to obtain the desired needle-shaped conductive tin oxide fine particles. Example 2 In the same manner as in Example 1, the desired needle-shaped conductive tin oxide fine particles were produced, but a sodium silicate aqueous solution of 34.9 m $ was used. Example 3 Using potassium chloride instead of sodium chloride, manufactured in the same way as in Example 1 (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210x297 mm) (%) 455568 A7 B7 Printed by Zhongli Standards Bureau of the Ministry of Economic Affairs—Industrial and Consumer Cooperatives. V. Description of the invention (1 Needed needle-shaped conductive tin oxide fine particles. Example 4 The same method as in Example 1 was used to obtain the required The required acicular conductive tin oxide fine particles were obtained by the method, but the calcination temperature was 1 QQ 0 ° C. The electron micrograph of the product is shown in Figure 1. Example 5 300 g of tetrachloropentahydrate A solution prepared by dissolving tin tin in an aqueous solution of 300 mj? 3 N hydrochloric acid and a sodium hydroxide solution having a concentration of 200 g / 5 were separately added at the same time at a temperature of 5 to 90 ° C. In pure water, the pH of the system is maintained at 7.0-8. 0 to produce a precipitate. Then, hydrochloric acid is added to adjust the system p Η to 3, after which the precipitate is filtered and washed with water until the filtrate The resistivity is up to 2 0 0 0 Ω cm. The formed cake is dried at 120 ° C for 12 hours, and then ground. Powder honing. Add 100 parts by weight of the honed product to 2.5 parts by weight of colloidal silica and 20 parts by weight of sodium chloride, and then mix to obtain a homogeneous mixture. The mixture Calcined in an electric furnace at 900 ° C for 1 hour. After that, the formed dried product was immersed in an aqueous solution of hydrofluoric acid to remove soluble salts, followed by drying and honing to obtain the desired needle-shaped conductive tin oxide fine particles. Example 6 ′ The needle-shaped conductive tin oxide fine paper required in the same manner as in Example 1 was used. The paper size was in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm). * ------ ^ (Please read the notes on the back before filling this page) A7 B7 V. Description of the invention (1 grain, but the amount of sodium chloride is 60 parts by weight. Comparative Example 1 Same as Conductive fine particles were produced by the method of Example 1, but sodium chloride was not used. Comparative Example 2 Conductive fine particles were produced by the same method as in Example 1, except that sodium silicate was not used. An electron micrograph of the product is shown in Figure 2. Comparative Example 3 Conductive fine particles were produced in the same manner as in Example 1, but the calcination temperature was 6 0 0 ° C. Example 7 A solution prepared by dissolving 500 g of tin tetrachloride pentahydrate and 3.36 g of antimony trichloride in a 3 N hydrochloric acid aqueous solution, 17.4 m_? Of the central standard of the Ministry of Economics of Silicic Acid Printed by Du Bureau's consumer cooperation (please read the precautions on the back before filling in this page) Sodium aqueous solution (3 0 8 g / S i 0 2 form) and sodium hydroxide solution are added separately within 20 minutes at the same time 5 Θ 9 0 ° C of pure water, keeping the pH of the system at 7-7. 5 to make a precipitate. Then, hydrochloric acid was added to adjust the system pΗ to 3, and then the precipitate was filtered and washed with water until the resistivity of the filtrate reached 15 00 nm. The formed cake was dried at 110 ° C for 12 hours, and 20 parts by weight of sodium chloride was added to 1 QQ by weight of dryness. This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) 21 455568 A7 B7 V. Description of the invention (1) The product is then uniformly mixed and honed. The mixture is calcined in an electric furnace at 900 ° C for 1 hour. Thereafter, the formed calcined product is immersed in a kind of hydrogen The soluble salt is removed from the hydrofluoric acid aqueous solution, and then dried and honed to obtain the required antimony-containing acicular conductive tin oxide fine particles. The particle color b_ 値 (filled under 200 kg / cm3 compressed particles) is one. 9. 4, whose 値 L * is 73.6. Example 8 The required antimony-containing needle-shaped conductive tin oxide fine particles were prepared in the same manner as in Example 7, but the amount of antimony trichloride was 10. lg Example 9 The required antimony-containing acicular conductive tin oxide fine particles were obtained in the same manner as in Example 7, except that a sodium silicate aqueous solution of 34.9 m $ was used. Example 10 Shenyang, Ministry of Economic Affairs Printed by the Consumer Bureau of Standards Bureau (please read the precautions on the back before filling this page). The desired antimony-containing acicular conductive tin oxide fine particles were used, but potassium chloride was used instead of sodium chloride. Example 11 1 The same method as in Example 7 of Tongyin was used to obtain the required antimony-containing acicular conductive tin oxide fine particles. Pellets, but its calcined product is 1000 ° C. The electron micrograph of this product is shown in Figure 3. This paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm), said 4 5 5 5 6 8 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ______B7_ 5. Description of the Invention (called Example 1 2 3 0 g of tin tetrachloride pentahydrate and 2.0 2 g of antimony trichloride were dissolved in 30 Omp The solution prepared in an aqueous solution of 3 N argon chloric acid and a sodium hydroxide solution having a concentration of 200 g / y are added separately to pure water at 590 ° C during 20 minutes to maintain the system. P p It is 7.0 to 8. 0 to produce a precipitate. Then, hydrochloric acid is added to adjust the system ρ Η to 3, and then the precipitate is filtered and washed with water until the resistivity of the filtrate is 20000 0 Up to ODcm. The formed cake was dried at 120 ° C for 12 hours, and then honed with a grinder. It was honed at 1 Q 0 parts by weight To this was added 2.5 parts by weight of colloidal silica and 20 parts by weight of sodium chloride, followed by mixing. The mixture was calcined in an electric furnace at 900 ° C for 1 hour. After that, the dried product formed Immerse in the hydrofluoric acid aqueous solution to remove the soluble salt, and then dry and hob it to obtain the desired antimony-containing needle-like conductive tin oxide fine particles. Example 1 3 Fine needle-shaped conductive tin oxide containing antimony, but the amount of sodium chloride was 6 (3 parts by weight. Comparative Example 4 Conductive fine particles were prepared in the same manner as in Example 7 except that sodium chloride was not used. 0 Comparative Example 5 ^ Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) _ μ _ --- ------ Install -------- Order ^ ------ ^ (Please read the notes on the back before filling this page) _ 5 556 8 A7 B7 V. Description of the invention (21) Same as The conductive fine particles prepared by the method of Example 7 did not use sodium silicate. An electron micrograph of the product is shown in FIG. 4. Comparative Example 6 Conductive fine particles were obtained in the same manner as in Example 7, except that 37 g of antimony trichloride was used. Comparative Example 7 Conductive fine particles were prepared by the method of Example 7 of Tongyin, but the calcination temperature was 600 ° C. Comparative Example 8 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Dissolve 234.5 g of tin tetrachloride pentahydrate and 15.6 g of antimony trichloride in 50 Omi? Solution prepared in 5 N hydrochloric acid aqueous solution, 9.7m aqueous solution of sodium silicate (308g / 5 in the form of SiO2) and sodium hydroxide solution were added at the same time separately within 30 minutes 5 and 9 Pure water at 0 ° C, keeping the pH of the system at 6-7 to make a co-precipitate of tin oxide, antimony oxide and silicon dioxide hydrate. Then, hydrochloric acid was added thereto to adjust the pH of the system to 3, and then the precipitate was filtered and washed with water until the resistivity of the filtrate reached 15 0 0 Ω cm. The formed cake was dried at 70 Q ° C for 4 hours, and the dried product was pulverized with a mill to obtain spherical fine particles having a specific surface area of 75.6 rrf / g. This paper size applies to China National Standard (CNS) A4 specification (2 丨 〇X 297 mm) 〇 ^ -24 A7 4 5 5 5 6 8 B7 V. Description of the invention (0 Example 1 4 (Please read the note on the back first) Please fill in this page again) A solution prepared by dissolving 500 g of tin tetrachloride pentahydrate in 50 OmJ? Of a 3N aqueous solution of hydrochloric acid, 17. 4 m {of sodium silicate aqueous solution (3 0 8 g / S i 〇2 form of j?) and sodium hydroxide solution at the same time individually added 5 ί 9 0 ° C pure water within 20 minutes, keeping the system at 7-7. 5 to make a precipitate. Then, hydrochloric acid was added to adjust the pH of the system to 3, and then the precipitate was filtered and washed with water until the resistivity of the filtrate reached 15 0 OQcni. The formed cake was at 1 1 0 ° C was dried for 12 hours, 20 parts by weight of sodium chloride was added to 100 parts by weight of the dried product, and then, the mixture was uniformly mixed and honed. The mixture was heated in an electric furnace at 90 ° C. Bake for 1 hour. After that, the formed calcined product is immersed in an aqueous hydrofluoric acid solution to remove soluble salts. Then, the formed cake is reconstituted in 5 pure water. It was made into a slurry and heated to 90 ° C. Then, 3.36 g of antimony trichloride (Sb / Sn atomic ratio of 1/1 0 0) was dissolved in 3 at the same time during 20 minutes. 0 0m $ 3N solution prepared in aqueous hydrochloric acid solution and sodium hydroxide solution, keep the system p Η 7 7.5 economic. Then the Central Bureau of Standards and staff consumption cooperation Du printed to deposit hydrated antimony oxide On acicular tin oxide. Then, add hydrochloric acid to adjust the system ρ Η 値 to 3, and then filter the precipitate and wash with water until the filtrate resistivity reaches 2 0 0 0 0 cm. The cake is formed on It was calcined in an electric furnace at 900 ° C for 1 hour and honed with a pulverizer to obtain the antimony-containing needle-shaped tin oxide fine particles of the present invention. Example I 5 This paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210X 297 mm) oc zb-A7 4 5 556 8-V. Explanation of the invention (23) The chain needle-like tin oxide fine particles of the present invention were prepared in the same manner as in Example 14, but after depositing hydrated antimony oxide, The filtered and burnt temperature of the reduced cake was 100 ° C. Example 16 The same method as in Example 14 was used to prepare the Acicular tin oxide fine particles, but the amount of antimony trichloride is 16. 8 2 g (S b / S η atomic ratio is 5/1 〇 〇). Test Example 1 Prepared by the above examples and comparative examples The conductive fine particle samples were constructed with the following measurements. (1) The weight average particle size was obtained by observing an electron micrograph (XI 0 0, 0 0 0), and the aspect ratio was also calculated from it. (2) The resistivity of the sample powder was measured with a digital multi meter under a pressure of 1000 k g / cm3: Model 2 50 2A manufactured by Yokogawa Hokushin Electric Cq. Ltd. The results are shown in Table 1. -1 im In ^^ 1 ^^ 1 I-----1 ^^^ 1-1 ^ 1 ---- (^ (Please read the precautions on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs The paper size printed by the employee consumer cooperative is applicable to China National Standard (CNS) A4 (210 X 29? Mm) 45 556 8 A7
7 B 五、發明説明（¥) 經濟部中央榡隼局員工消費合作社印製 表 1 顆粒形狀和大小（μ m ) 粉末 電阻 平均直徑 平均長度 縱横tb 實施例1 0.010 0.20 20 9.2 k Ω cm 〃 2 0.012 0.23 19 5.3 k Ω cm ” 3 0.010 0.25 25 7.6 k Ω cm /' 4 0.015 0.48 32 2.1 k Ω era // 5 0.013 0.07 5 9.3 k Ω cm ff 6 0.011 0.15 11 5.1 k Ω cm 對照實例1 非針狀 12.1 k Ω era 〃 2 // 10.9 kΩ cm '， 3 ff 51.2 k Ω cm 實施例7 0.011 0.50 45 4.6 k Ω cm 〃 8 0.013 0.23 18 2.0 k Ω cm η 9 0.015 0.57 38 4.5 k Ω cm // 10 0.011 0.30 27 4.7 k Ω cm 〃 11 0.020 1.20 60 2,6 k Ω cm n 12 0,015 0.17 11 4.9 k Ω era // 13 0.012 0.38 32 6.0 kΩ cm 對照實例4 非針狀 3,6 kΩ cm 〃 5 〃 2.0 k Ω cm Ί 6 // 1.8 k Ω cm η 7 η 100 kΩ cm !' 8 it 2.1 k Ω cm 實施例1 4 0.015 0.50 33 18.5 kO cm 〃 1 5 0.024 0.52 22 31.7 kΩ cm ” 16 0.014 0.50 36 8.0 kΩ cm (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐> 4 5 5 5 6 8 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（2$ 試驗實例2 將實施例1和7與對照實例2 ，5和8製得之導電性 細粒個別（每種20g)與30. 6g之丙烯酸樹脂（ Dainippon Ink & Chemical inc.)製，固體含量 4 5 重量％之八匚尺丫〇1〇八一165-45)，26.4 g之甲酮一 丁醇混合溶液（混合重量比率1 : 1)，及 5 0 g之玻璃珠混合。然後，形成之混合物以一塗料搖動 器（由 Red Devil Co., Ltd 製之 #5 1 1 0 )搖動 2 0 分鐘，製得一種碾磨基質。 然後於每種碾磨基質中個別加入上述給定數量之丙烯 酸樹脂和甲酮_ 丁醇混合溶液，隨後攪拌並混合以製備顏 料濃度（w t %)如表2所示之塗料。將該塗料塗覆於一 種乾燥膜厚度爲4 〃 m之聚酯膜，且於空氣乾燥4 0小時 得到一試驗板。該板表面電阻率（Ω/ 口）係以數位化歐 姆計測量：Kwaguchi Deu Ki Mfg. Co.，Ltd.製之 R — 5 0 6 ° 此外，以一濁度計測量濁度：Nippon Deushoku Kogyo Co., Ltd 製之 NDH : 3 0 0 A 0 結果示於表2和表3。 I I I H 裝 I I I —訂 I I t>J (請先閱讀背面之注意事項再填寫本頁) _ 本紙張尺度適用中國國家標準（CMS ) A4規格（2!OX297公釐） -28 - 4 經濟部t央標隼局—工消費合作杜印製 5 556 8 A7 B7 五、發明説明（叫 表 2 — 1 顏料濃度 導電性材料 表面電阻率（Ω/口） 3 0 w t % 4 0 w t % 5 0 w t % 實施例1 1 . 5 X 1 0 1 1 1 . 9 X 1 0 1 1 1 . 3 X 1 0 1 1 對照實例2 高於1014 1 . 5 X 1013 6.6X 1011 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（C'NS ) A4規格（210X297公釐）_ 9g 4 5 5 5 6 8 A7 經濟部中央標隼局員工消費合作社印掣 五、發明説明（2?) 表 2-2 表面電阻率（Ω/口； 顏料濃度 導電性材料 1 5 w t % 2 0 w t % 2 5 w t % 實施例7 1 . 7 X 1 0 1 0 2 . 3 X 109 1.5 X 1 09 對照實例5 高於1014 高於1 0 1 4 高於1 014 對照實例8 高於1014 高於10 1 4 高於1014 (請先閲讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家標準（C'NS ) A4規格（2j〇X 297公釐） 30 A7 經濟部中央標準局員工消費合作社印製 ,b 5 6 8 B7 五、發明説明（28) 表 3-1 顏料濃度 導電材料 濁度（％ ) 3 0 w t % 4 0 w t % 5 0 w t % 實施例1 4 7 6 1 7 4 對照實例2 4 6 5 7 7 0 --------裝------^訂 l·----I ^ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 29<7公釐） 31 A7 B7 4bb56 8 五、發明説明（29) 表 3 — 2 顏料濃度 導電材料 濁度（％ ) 1 5 w t % 2 0 w t % 2 5 w t % 實施例7 2 5.2 3 2.2 3 9.4 對照實例5 2 3.5 3 1.2 3 7.3 對照實例8 2 1.4 2 9.5 3 5.6 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 試驗實例3 將贲施例1 4 ，1 5和1 6中製得之導電性細粒樣本 個別於2 0 Ok g/cirf壓力下成形，製成柱狀緊密粉 末（直徑3 3 mm，厚度5 mm)且該粉末顏色係由Suga Mig. Cq. Ltd.製之顏色計算器SM - 7 - I S_ 2 B 測量。結果示於表4。該粉未顏色之値L _和値b |表示 於 Commission Internatikonale d e I 1 E c 1 a i r a g e 中之 本紙張尺度適用中國國家標準（CNsTa4規格（210X297公釐）_ _ 455568 A7 B7 經濟部中央標率扃員工消費合作社印製 五、發明説明（3〇) C I E 1 9 7 6 L'a'b.顏色空間之亮度指數和顏色 指數。 表 4 粉末顔色 b ' L . // 1 A -5.8 8 2.3 // 1 5 -4 . 6 8 5.9 // 1 6 — 6.0 8 1.0 本發明提出針狀導電性細粒或一種含銻之針狀導電性 細粒，其添加比慣用導電性細粒更少之數量，但可提供良 好之傳導性，及不使用特殊裝置和昂貴原材料製造該細粒 之方法。此外，本發明含錄之針狀導電性細粒粉未電阻明 顯地低於塗覆有含氧化錫和氧化銻導電層之鈦酸鉀纖維。 此外，含本發明細粒之樹脂組成物或黏合劑具有非常優良 之傳導性和優良之透明度。特別是，直徑爲〇· 0ΰ5_ 本紙張尺度適用中國國家標準（CNS) A4規格（2丨OX297公釐）_ n nn n (請先閱讀背面之注意事項再填寫本頁)7 B V. Description of the invention (¥) Printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economy Table 1 Particle shape and size (μm) Average diameter of powder resistors Average length vertical and horizontal tb Example 1 0.010 0.20 20 9.2 k Ω cm 〃 2 0.012 0.23 19 5.3 k Ω cm ”3 0.010 0.25 25 7.6 k Ω cm / '4 0.015 0.48 32 2.1 k Ω era // 5 0.013 0.07 5 9.3 k Ω cm ff 6 0.011 0.15 11 5.1 k Ω cm Comparative Example 1 Non-needle 12.1 k Ω era 〃 2 // 10.9 kΩ cm ', 3 ff 51.2 k Ω cm Example 7 0.011 0.50 45 4.6 k Ω cm 〃 8 0.013 0.23 18 2.0 k Ω cm η 9 0.015 0.57 38 4.5 k Ω cm // 10 0.011 0.30 27 4.7 k Ω cm 〃 11 0.020 1.20 60 2,6 k Ω cm n 12 0,015 0.17 11 4.9 k Ω era // 13 0.012 0.38 32 6.0 kΩ cm Comparative example 4 Non-acicular 3,6 kΩ cm 〃 5 〃 2.0 k Ω cm Ί 6 // 1.8 k Ω cm η 7 η 100 kΩ cm! '8 it 2.1 k Ω cm Example 1 4 0.015 0.50 33 18.5 kO cm 〃 1 5 0.024 0.52 22 31.7 kΩ cm ”16 0.014 0.50 36 8.0 kΩ cm (Please read the notes on the back before filling this page) This paper size is applicable to China Home Standard (CNS) A4 Specification (210X297 mm > 4 5 5 5 6 8 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (2 $ Test Example 2 Example 1 and 7 and Comparative Example The conductive fine particles prepared in 2, 5 and 8 were individually made (20 g each) and 30.6 g made of acrylic resin (Dainippon Ink & Chemical inc.), With a solid content of 45 wt. Bayi 165-45), 26.4 g of a ketone-butanol mixed solution (mixed weight ratio 1: 1), and 50 g of glass beads were mixed. Then, the resulting mixture was shaken with a paint shaker (# 5 1 1 0 manufactured by Red Devil Co., Ltd) for 20 minutes to prepare a milled substrate. Then, each of the milled substrates was individually added with the above-mentioned given amounts of the acrylic resin and ketone-butanol mixed solution, followed by stirring and mixing to prepare paints having a pigment concentration (wt%) as shown in Table 2. This coating was applied to a polyester film having a dry film thickness of 4 μm, and air-dried for 40 hours to obtain a test plate. The surface resistivity (Ω / mouth) of this board was measured with a digital ohmmeter: R — 5 0 6 ° by Kwaguchi Deu Ki Mfg. Co., Ltd. In addition, the turbidity was measured with a turbidity meter: Nippon Deushoku Kogyo The results of NDH: 3 0 0 A 0 manufactured by Co., Ltd are shown in Tables 2 and 3. IIIH Pack III — Order II t &J; (Please read the notes on the back before filling this page) _ This paper size is applicable to China National Standard (CMS) A4 specification (2! OX297 mm) -28-4 The Central Ministry of Economic Affairs Standards Bureau-Industrial-Consumer Cooperation Du printed 5 556 8 A7 B7 V. Description of the invention (called Table 2 — 1 Pigment concentration Surface resistivity of conductive material (Ω / mouth) 3 0 wt% 4 0 wt% 5 0 wt% Example 1 1.5 X 1 0 1 1 1. 9 X 1 0 1 1 1. 3 X 1 0 1 1 Comparative Example 2 higher than 1014 1. 5 X 1013 6.6X 1011 (Please read the precautions on the back before (Fill in this page) This paper size applies the Chinese National Standard (C'NS) A4 (210X297 mm) _ 9g 4 5 5 5 6 8 A7 Printed by the Consumers' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (2? ) Table 2-2 Surface resistivity (Ω / mouth; pigment concentration conductive material 15 wt% 2 0 wt% 2 5 wt% Example 7 1. 7 X 1 0 1 0 2. 3 X 109 1.5 X 1 09 Comparative example 5 higher than 1014 higher than 1 0 1 4 higher than 1 014 Comparative example 8 higher than 1014 higher than 10 1 4 higher than 1014 (Please read the precautions on the back before filling this page) Order This paper size applies to the Chinese National Standard (C'NS) A4 (2j0X 297 mm) 30 A7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, b 5 6 8 B7 V. Description of Invention (28) Table 3- 1 Pigment concentration conductive material turbidity (%) 3 0 wt% 4 0 wt% 50 wt% Example 1 4 7 6 1 7 4 Comparative Example 2 4 6 5 7 7 0 ----- ^ Order l · ---- I ^ (Please read the notes on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 X 29 < 7 mm) 31 A7 B7 4bb56 8 V. Description of the invention (29) Table 3 — 2 Pigment concentration Conductive material turbidity (%) 1 5 wt% 2 0 wt% 2 5 wt% Example 7 2 5.2 3 2.2 3 9.4 Comparative example 5 2 3.5 3 1.2 3 7.3 Comparative Example 8 2 1.4 2 9.5 3 5.6 (Please read the precautions on the back before filling out this page) Printed Test Example 3 by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Example 3 will be implemented in Examples 1, 4, 5 and 1 The conductive fine-grain samples prepared in 6 were individually shaped under a pressure of 20 Ok g / cirf to form a columnar compact powder (33 mm in diameter and 5 mm in thickness), and the color of the powder was Suga Mig. Color calculator SM-7-I S_ 2 B made by Cq. Ltd. The results are shown in Table 4.粉 L _ and 値 b of this powder without color | The paper size indicated in the Commission Internatikonale de I 1 E c 1 airage is applicable to the Chinese national standard (CNsTa4 specification (210X297 mm) _ 455568 A7 B7 Central standard of the Ministry of Economic Affairs印 Printed by Employee Consumer Cooperatives V. Description of the invention (30) CIE 1 9 7 6 L'a'b. Brightness index and color index of color space. Table 4 Powder color b 'L. // 1 A -5.8 8 2.3 // 1 5 -4. 6 8 5.9 // 1 6 — 6.0 8 1.0 The present invention proposes needle-like conductive fine particles or a needle-like conductive fine particles containing antimony, the addition of which is less than the conventional conductive fine particles. Quantity, but can provide good conductivity, and a method for manufacturing the fine particles without using special equipment and expensive raw materials. In addition, the needle-shaped conductive fine particles contained in the present invention have a significantly lower electrical resistance than those coated with oxide Potassium titanate fiber with tin and antimony oxide conductive layer. In addition, the resin composition or adhesive containing the fine particles of the present invention has very good conductivity and excellent transparency. In particular, the diameter is 0 · 0ΰ5_ This paper size applies to China National Standard (CNS) A4 Grid (2 Shu OX297 mm) _ n nn n (Please read the Notes on the back to fill out this page)
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A 4 5 5 5 6 8 A7 B7 五、發明説明（31) 〇- 〇 5 //m之較細顆粒透明性優良。其者，含鍊之针狀 導電性細粒可藉於具有些微藍色調且亮度高，透明度和胃 導性佳之針狀氧化錫細粒上澱積水合氧化銻製得。 經濟部中央標準局員工消費合作社印製 準 標 家 國 國 I中 用 適 度 尺 張 紙一本 I釐 公 7 9 2A 4 5 5 5 6 8 A7 B7 V. Description of the invention (31) 〇- 〇 5 // m Fine particles have excellent transparency. Among them, acicular conductive fine particles containing chains can be obtained by depositing hydrated antimony oxide on acicular tin oxide fine particles having a slight blue tint and high brightness, transparency and gastric conductivity. Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs.